CN111848553A - Method for catalytically synthesizing gamma-valerolactone by cobalt-based hydrogenation catalyst - Google Patents
Method for catalytically synthesizing gamma-valerolactone by cobalt-based hydrogenation catalyst Download PDFInfo
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- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 title claims abstract description 142
- 239000003054 catalyst Substances 0.000 title claims abstract description 108
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 41
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 33
- 239000010941 cobalt Substances 0.000 title claims abstract description 33
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 9
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000000047 product Substances 0.000 claims abstract description 45
- UAGJVSRUFNSIHR-UHFFFAOYSA-N Methyl levulinate Chemical compound COC(=O)CCC(C)=O UAGJVSRUFNSIHR-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000003197 catalytic effect Effects 0.000 claims abstract description 21
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 238000000926 separation method Methods 0.000 claims abstract description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 29
- 239000002253 acid Substances 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 229910006213 ZrOCl2 Inorganic materials 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 9
- 239000012065 filter cake Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000005054 agglomeration Methods 0.000 claims description 5
- 230000002776 aggregation Effects 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 5
- -1 oxygen ion Chemical class 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000002950 deficient Effects 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 230000003993 interaction Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical class [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000000969 carrier Substances 0.000 claims description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- 238000003837 high-temperature calcination Methods 0.000 claims description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 230000005012 migration Effects 0.000 claims description 2
- 238000013508 migration Methods 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- 230000008929 regeneration Effects 0.000 claims description 2
- 238000011069 regeneration method Methods 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 abstract description 7
- 239000012263 liquid product Substances 0.000 abstract 1
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 12
- 238000003795 desorption Methods 0.000 description 10
- 241000894007 species Species 0.000 description 7
- 229940040102 levulinic acid Drugs 0.000 description 6
- 230000009467 reduction Effects 0.000 description 5
- 239000002028 Biomass Substances 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000002551 biofuel Substances 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 241000272201 Columbiformes Species 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/32—Oxygen atoms
- C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/847—Vanadium, niobium or tantalum or polonium
- B01J23/8474—Niobium
-
- B01J35/51—
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- B01J35/613—
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- B01J35/633—
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- B01J35/647—
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention discloses a cobalt-based hydrogenation catalyst Co/ZrO2‑Nb2O5The method for synthesizing gamma-valerolactone by catalyzing methyl levulinate hydrogenation has the advantages of high catalytic activity, good reusability, difficult loss of active components, easy separation from liquid products and the like, and when the mass ratio of the catalyst to the reaction raw material methyl levulinate to the reaction solvent isopropanol is 0.2:1:20, the reaction temperature is 200 ℃, and the reaction time is 2 hours, the hydrogenation product gamma-valerolactone molar yield is 98.32%, and the product purity mass percentage is 99.01%.
Description
Technical Field
The invention belongs to the field of biomass catalysis, and relates to a cobalt-based hydrogenation catalyst Co/ZrO2-Nb2O5A method for synthesizing gamma-valerolactone by catalyzing methyl levulinate.
Background
Biomass as renewable supportThe continuous organic molecules have wide sources and low price, and can be used for producing biofuel, high value-added chemicals and the like. Levulinic acid and esters thereof are biomass-based platform compounds, can be obtained by acidic hydrolysis of lignocellulose and the like in crop straws, and can be subjected to catalytic hydrogenation to obtain another biomass-based chemical gamma-valerolactone. The gamma-valerolactone has the characteristics of high boiling point, difficult volatilization, good solubility, high stability, low toxicity, degradability, easy storage and the like, can be used as a resin solvent, an intermediate of biofuel, polymer and fine chemical engineering, can also be used as a lubricant, a plasticizer, a gelling agent of a nonionic surfactant and a lactone additive of leaded gasoline, and can also be used for dyeing cellulose ester and synthetic fibers. Manzer et al studied the hydrogenation of levulinic acid into gamma-valerolactone by loading different metals Ir, Rh, Pd, Ru, Pt, Re and Ni on activated carbon, and found that when the levulinic acid reacts for 4 hours in a dioxane solvent at 150 ℃ and under the hydrogen pressure of 5.5MPa, the Ru/C activity is the best, the conversion rate of the levulinic acid is 100%, and the selectivity of the gamma-valerolactone is 97%, but the Ru cost is high and the catalytic activity is easy to decrease (Catal.A 272(2004) 249-doped 256). Cu/ZrO for pigeon in field and the like2The gamma-valerolactone is synthesized by catalyzing methyl levulinate through hydrogenation, the molar yield of the gamma-valerolactone is 75%, but metal Cu is easy to leach out, and the molar yield of the gamma-valerolactone is reduced to 53% after the catalyst is repeatedly used for three times (CataCommun 2016,76, 50-53). The subject group also prepared Ni/CeO2-ZrO2The gamma-valerolactone is synthesized by catalyzing levulinic acid to be hydrogenated and reacts for 6 hours at 180 ℃ and under the hydrogen pressure of 2.8MPa, so that the molar yield of the gamma-valerolactone is 97.6 percent, but the molar yield of the gamma-valerolactone is reduced to 54.5 percent after the catalyst is repeatedly used for three times. Co/La for G.Kasar et al2O3The levulinic acid is catalyzed to carry out hydrogenation reaction, when the reaction is carried out for 5 hours at 200 ℃ and under the hydrogen pressure of 3.4MPa, the gamma-valerolactone molar yield is 78%, but after the catalyst is repeatedly used for three times, the gamma-valerolactone molar yield is reduced to 63% (Energy Fuels 2018,32,6887 and 6900).
Aiming at the problems of easy leaching of metal active components, long reaction time, poor stability and the like of the catalyst, the cobalt-based hydrogenation catalyst Co/ZrO prepared by the invention2-Nb2O5Catalyzing methyl levulinate hydrogenation by using isopropanol as hydrogen sourceAnd reacting for 2 hours at 200 ℃ to obtain the gamma-valerolactone with the molar yield of 98.32 percent and the purity of 99.01 percent, and recycling the catalyst for 10 times through vacuum drying, wherein the molar yield of the gamma-valerolactone is still kept at 95.83 and the purity of 96.59 percent.
Disclosure of Invention
Objects of the invention
The invention aims to provide a cobalt-based catalyst Co/ZrO2-Nb2O5A method for synthesizing gamma-valerolactone by catalyzing methyl levulinate.
Technical scheme of the invention
1. A method for catalytically synthesizing gamma-valerolactone by using a cobalt-based hydrogenation catalyst is characterized by comprising the following steps of:
(1) the cobalt-based hydrogenation catalyst is Co/ZrO2-Nb2O5Wherein the mass percent of the active component Co is 10 percent, ZrO2-Nb2O5The molar ratio of Nb to Zr in the carrier is 0.2-0.25: 1;
the cobalt-based hydrogenation catalyst is of a spherical mesoporous structure, the aperture is 10-15 nm, and the pore volume is 0.16-0.24 cm3A specific surface area of 52 to 75 m/g2/g；
The cobalt-based hydrogenation catalyst Co/ZrO2-Nb2O5Medium, ZrO2Has rich oxygen vacancy and low-coordination oxygen ion, and passes through H before the catalyst is used2Reduced, reduced active component Co attracts ZrO2The oxygen atom on the ZrO undergoes a migration change to attract the ZrO2The oxygen on the catalyst activates Zr-O-Zr bonds to form-O-Zr vacancies, so that the surface of the catalyst is in a relative electron-deficient state, and the surface of the catalyst in the relative electron-deficient state can effectively activate the hydrogenation of C ═ O groups in methyl levulinate molecules in the process of catalyzing the hydrogenation of methyl levulinate to synthesize gamma-valerolactone;
the cobalt-based hydrogenation catalyst Co/ZrO2-Nb2O5Nb with large acid content and strong acidity2O5ZrO of metal oxide doped with acid-base amphiprotic2ZrO formed2-Nb2O5The carrier increases the acidic sites and acids of the catalystAmount, Co/ZrO undoped with Nb2Acid amount of 3.75mmol/g, Co/ZrO after Nb doping2-Nb2O5The acid amount of (a) is 4.95 mmol/g;
the cobalt-based hydrogenation catalyst Co/ZrO2-Nb2O5Nb species in the active components Co and ZrO2-Nb2O5The interaction between carriers inhibits the agglomeration of the active component Co and the carbon deposition sintering, and improves the dispersion degree of the active component Co, and the comparison of the attached drawings 2(a) and (b) in the specification shows that the active component Co is compared with Co/ZrO2Co/ZrO after Nb doping2-Nb2O5The active component Co is uniformly dispersed, and no obvious agglomeration phenomenon exists;
the cobalt-based hydrogenation catalyst Co/ZrO2-Nb2O5In the medium, the doped Nb species makes ZrO2The crystal lattice is distorted to form ZrO2More oxygen vacancies are generated, the cationic oxophilic site formed by the doped Nb species and the carbonyl oxygen in the methyl levulinate generate stronger interaction to weaken the C ═ O bond, the energy required by the C ═ O double bond in the methyl levulinate to break is reduced, and the catalytic hydrogenation performance is enhanced: example 10 the results show Co/ZrO undoped with Nb2The mole yield of the catalytic methyl levulinate hydrogenation product gamma-valerolactone is 62.02%, and the result of example 1 shows that the Co/ZrO after doping Nb2-Nb2O5The molar yield of the catalytic methyl levulinate hydrogenation product gamma-valerolactone is 98.32%;
the cobalt-based hydrogenation catalyst Co/ZrO2-Nb2O5After the catalytic methyl levulinate hydrogenation reaction, recovering the catalytic methyl levulinate through simple centrifugal separation, and drying the catalytic methyl levulinate in a drying oven at the temperature of 60-80 ℃ and the vacuum degree of 100-133 Pa for 1-2 hours to obtain the catalytic methyl levulinate which can be used as a catalyst for the next repeated use without high-temperature calcination regeneration;
compared with the reported Ru/C, Cu/ZrO2、Ni/CeO2-ZrO2、Co/La2O3The catalyst activity is greatly reduced after the catalyst is repeatedly used for 3 times, and the results of example 29 show that the Co-based hydrogenation catalyst Co/ZrO2-Nb2O5Can be repeatedly used for 10 times and still has better catalysisThe activity, the mole yield of the gamma-valerolactone of the catalytic methyl levulinate hydrogenation product is still kept at 95.83%;
(2) the Co-based hydrogenation catalyst Co/ZrO as described in (1)2-Nb2O5Is prepared by the following method:
the first step is as follows: mixing Nb (HC)2O4)5And ZrOCl2·8H2Adding deionized water according to the molar ratio of 0.2-0.25: 1 into the O, stirring and dissolving to form a mixed solution with the total molar concentration of 0.10-0.15 mol/L, slowly adding ammonia water to control the pH value of the mixed solution to be within the range of 11-14, and stirring at room temperature for 30-40 min to obtain a mixed solution containing white precipitates;
the second step is that: transferring the mixed solution containing the white precipitate into a polytetrafluoroethylene lining, crystallizing at 170-180 ℃ for 6-8 h, cooling to room temperature, carrying out suction filtration and precipitation, washing a filter cake to be neutral by using deionized water, drying the obtained white powdery filter cake at 80-110 ℃ for 6-8 h, placing the white powdery filter cake in a box-type muffle furnace, raising the temperature to 450-500 ℃ at the rate of 2-3 ℃/min, roasting for 4-6 h, and cooling to obtain the ZrO2-Nb2O5A carrier;
the third step: mixing Co (NO)3)2·6H2O, ZrO prepared as described above2-Nb2O5Adding a carrier and an impregnant into a reactor according to a mass ratio of 0.1-0.2: 1: 15-20, soaking and stirring for 6-8 hours at 40-60 ℃, and evaporating and recovering the impregnant at 40-60 ℃ to obtain light purple powder, wherein the impregnant is absolute methanol or absolute ethanol;
the fourth step: drying the light purple powder at the constant temperature of 60-80 ℃ for 4-6 h, placing the dried light purple powder in a box-type muffle furnace, raising the temperature to 350-450 ℃ at the heating rate of 2-3 ℃/min, roasting the dried light purple powder for 4-6 h, and cooling the roasted light purple powder to obtain black powder, namely the cobalt-based hydrogenation catalyst Co/ZrO2-Nb2O5；
The prepared cobalt-based hydrogenation catalyst Co/ZrO2-Nb2O5Placing the mixture in a tubular furnace, raising the temperature to 450-500 ℃ at a heating rate of 3-5 ℃/min and keeping the temperature for 2 hours under the atmosphere of hydrogen flow rate of 45-55 mL/min,after cooling, the mixture is placed in N2Passivating in an atmosphere for use in N2The catalytic activity of the catalyst can be effectively maintained for 45-60 days in the atmosphere;
(3) Co/ZrO from the cobalt-based hydrogenation catalyst described in (1)2-Nb2O5The method for synthesizing gamma-valerolactone by catalyzing methyl levulinate comprises the following steps:
Co/ZrO based hydrogenation catalyst2-Nb2O5Adding a reaction raw material methyl levulinate and a reaction solvent in a mass ratio of 0.1-0.2: 1:20 into a reactor, uniformly mixing, heating to 220-240 ℃ for reaction for 2 hours, recovering the reaction solvent from a reaction system after the reaction is finished, centrifugally separating a lower-layer catalyst to obtain a product gamma-valerolactone, wherein the molar yield of the product gamma-valerolactone is 95-98.8%, the purity is 96.5-99%, precipitating and filtering the lower-layer catalyst after centrifugal separation, washing the precipitated and filtered catalyst with isopropanol, and performing vacuum drying to obtain the catalyst which can be used as the catalyst for next repeated use;
the reaction solvent is isopropanol and simultaneously serves as a reaction raw material hydrogen source, and is evaporated and recovered at the temperature of 80-85 ℃ under the condition of vacuum pumping of 0.084-0.0848 MPa after the reaction is finished, and the cooled reaction solvent is recycled.
Technical advantages and effects of the invention
1. The cobalt-based hydrogenation catalyst Co/ZrO of the invention2-Nb2O5The catalyst has high catalytic activity and short reaction time, is easy to separate from a reaction system, and when the catalyst is used for catalyzing the hydrogenation reaction of methyl levulinate to synthesize gamma-valerolactone, the molar yield of the product gamma-valerolactone is 98.32 percent and the purity is 99.01 percent when the mass ratio of the catalyst to the methyl levulinate to the reaction solvent isopropanol is 0.2:1:20 and the reaction is carried out for 2 hours at 200 ℃.
2. The cobalt-based hydrogenation catalyst Co/ZrO of the invention2-Nb2O5After centrifugal separation and recovery, the gamma-valerolactone is reused for 10 times after vacuum drying treatment, and the products of the gamma-valerolactone still have the molar yields of 95.83 percent and 96.59 percent and good reusability.
3. The isopropanol is used as a reaction solvent and a hydrogen source, so that the hydrogen utilization rate is high, the operation is safe, the recovery is easy, and the transportation is convenient.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) picture in which (a) is ZrO2-Nb2O5A carrier, wherein the molar ratio of Nb to Zr in the carrier is 0.25:1, and (b) is Co/ZrO with 10 percent of Co mass2-Nb2O5A catalyst. FIG. 1(a) shows ZrO2-Nb2O5The support has a spherical structure, and FIG. 1(b) shows that in ZrO2-Nb2O5When Co is supported on the carrier, a granular porous structure is formed, and the surface is rough and uneven.
FIGS. 2(a) and (b) are Co/ZrO with 10% Co by mass2-Nb2O5(Nb to Zr molar ratio 0.25:1), Co/ZrO2High Resolution Transmission Electron Microscopy (HRTEM) images of the samples. As is clear from comparison of FIGS. 2(a) and (b), Co in FIG. 2(a) adheres uniformly to ZrO as compared with FIG. 2(b)2-Nb2O5The carrier has good surface and dispersion degree, and has no obvious agglomeration phenomenon. Fast Fourier Transform (FFT) was performed on the image, and lattice spacings of the facets were found to be 0.28nm, 0.36nm, and 0.29nm, corresponding to monoclinic phase ZrO, respectively2(111) Crystal face and tetragonal phase ZrO (011)2(011) Crystal planes, no lattice lines of the Nb phase appear, which is due to the too low content of the Nb phase.
FIG. 3 shows ZrO at a Nb to Zr molar ratio of 0.25:12-Nb2O5XRD patterns of Co loaded on the carrier with different mass percentages, wherein (a) is ZrO2-Nb2O5The carriers (b), (c), (d) and (e) are Co/ZrO with Co loading of 5%, 10%, 15% and 20% by mass respectively2-Nb2O5A sample of the catalyst. As can be seen from fig. 3, monoclinic phase ZrO is at 24.4 °, 28.17 °, 31.46 °, 34.16 ° (PDF #37-1484) at 2 θ ═ 24.4 °, 31.46 °, and2(m-ZrO2) The diffraction peaks correspond to characteristic diffraction peaks of (011), (111) and (200) crystal planes respectively. Diffraction peaks at 2 θ of 30.3 °, 50.4 °, and 60.2 ° (PDF #50-1089) are respectively ascribed to tetragonal ZrO2(t-ZrO2) Crystal planes (011), (112), and (121) of (A). The diffraction peak at 2 theta 44.3 ° (PDF #15-0806) corresponds to Co0(111) A crystal plane of (a). Diffraction of Nb phase was not observed in the figurePeaks due to the low content of this phase and the uniform distribution in the support. From the comparison of fig. 2(b), (c), (d) and (e), the intensity of the characteristic Co peak increases with the increase of the Co loading amount, and when the Co mass percentage is less than 10%, the characteristic Co peak does not appear, which indicates that the metal Co is uniformly distributed in the catalyst.
FIG. 4(a) is Co/ZrO2And (b) is Co/ZrO2-Nb2O5(Nb and Zr mol 0.25:1), (c) is Co/ZrO2-Nb2O5(Nb to Zr molar ratio 0.43:1), (d) is Co/ZrO2-Nb2O5(Nb to Zr molar ratio 2.3:1), (e) Co/Nb2O5XRD patterns of the samples, the mass percent of Co in these samples was 10%. As can be seen from comparison of fig. 4(a), (b), (c), (d), and (e), when the content of the Nb-doped species in the sample is low, m-ZrO is 28.2 ° and 31.46 ° in 2 θ2The phase diffraction peak intensity becomes strong, and t-ZrO at 2 theta of 30.3 DEG and 50.4 DEG2The diffraction peak intensity of the phase is weakened, and meanwhile, a Co characteristic peak does not appear, namely Co is uniformly dispersed in the carrier. With the increase of the content of the doped Nb species, a wider dispersion type diffraction peak is firstly generated to indicate that an amorphous structure is formed, and a Co characteristic peak is generated to indicate that Co is slightly sintered and agglomerated, and the agglomeration of particles can reduce the crystallinity, so that the X-ray diffraction peak intensity is weakened.
FIG. 5(a) is Co/ZrO2And (b) is Co/ZrO2-Nb2O5(Nb to Zr molar ratio 0.25:1) H of sample2TPR diagram, the mass percentage of Co in the sample being 10%. As can be seen from FIG. 5, Co/ZrO2-Nb2O5The reduction peak at around 300 ℃ is assigned to Co3O4Reduction to CoO, with the reduction peaks at around 400 ℃ from CoO to Co0Reduction of (2); and Co/ZrO2In the range below 450 ℃ there is only one reduction peak, representing Co3O4To Co0And (4) carrying out one-step reduction. Neither catalyst exhibited a reduction peak above 500 ℃, indicating that doping with Nb species did not result in the presence of difficult to reduce cobalt species in the catalyst.
FIG. 6(a) is Co/ZrO2And (b) is Co/ZrO2-Nb2O5(Nb to Zr molar ratio 0.25:1) NH of sample3TPD plot, wherein the mass percentage of Co in the samples is 10%. At NH3In the graph of-TPD, a low-temperature desorption peak (T25-250 ℃) corresponds to a weak acid center, a medium-temperature peak (T250-400 ℃) corresponds to a medium-strong acid center, and a high-temperature peak (T)>400 ℃ C.) corresponds to a strong acid center. As can be seen from FIG. 6, the desorption peak at a temperature within 250 ℃ is a weak acid site desorption peak, the desorption peak at about 400 ℃ is a medium acid site desorption peak, and the desorption peak at about 650 ℃ is a strong acid site desorption peak. As is clear from comparison of FIGS. 6(a) and (b), when the Nb phase is doped, one more desorption peak is observed at each of the weak acid site (250 ℃) and the medium-strong acid site (350 ℃), one less desorption peak is observed at the strong acid site at 550 ℃, and the desorption peak intensities are increased at the medium-strong acid (400 ℃) and the strong acid (650 ℃). Overall, the incorporation of Nb results in an increased amount of catalyst acid.
The technical solution and the implementation mode of the present invention are described below by way of examples, but not limited to the following examples.
Example 1
1. Co/ZrO based hydrogenation catalyst2-Nb2O5Preparation of
The first step is as follows: mixing Nb (HC)2O4)5And ZrOCl2·8H2Adding deionized water according to the molar ratio of 0.25:1 into the O, stirring and dissolving to form a mixed solution with the total molar concentration of 0.15mol/L, slowly adding ammonia water to control the pH value of the mixed solution to be 13, and stirring at room temperature for 30min to obtain a mixed solution containing white precipitates;
the second step is that: transferring the mixed solution containing the white precipitate into a polytetrafluoroethylene lining, crystallizing at 180 ℃ for 6h, cooling to room temperature, carrying out suction filtration on the precipitate, washing the filter cake to be neutral by using deionized water, drying the obtained white powdery filter cake at 80 ℃ for 6h, then placing the white powdery filter cake in a box-type muffle furnace, raising the temperature to 450 ℃ at the rate of 2 ℃/min, roasting for 6h, and cooling to obtain ZrO2-Nb2O5A carrier;
the third step: mixing Co (NO)3)2·6H2O, ZrO prepared as described above2-Nb2O5Adding a carrier and an impregnant into a reactor according to the mass ratio of 0.1:1:20, impregnating and stirring for 8 hours at 45 ℃, and evaporating and recovering the impregnant at 50 ℃ to obtain light purple powder, wherein the impregnant is absolute ethyl alcohol;
the fourth step: drying the light purple powder at the constant temperature of 80 ℃ for 6h, putting the dried light purple powder in a box-type muffle furnace, raising the temperature to 450 ℃ at the heating rate of 2 ℃/min, roasting the dried light purple powder for 6h, and cooling the roasted light purple powder to obtain black powder, namely the cobalt-based hydrogenation catalyst Co/ZrO2-Nb2O5；
The fifth step: the prepared cobalt-based hydrogenation catalyst Co/ZrO2-Nb2O5Placing in a tube furnace, heating to 500 deg.C at a temperature rise rate of 5 deg.C/min under hydrogen flow rate of 45mL/min, maintaining for 2 hr, cooling, and placing in N2Passivating in an atmosphere for use in N2The catalytic activity of the catalyst can be effectively maintained for 60 days in the atmosphere.
2. Catalytic methyl levulinate hydrogenation reaction
Co/ZrO based hydrogenation catalyst2-Nb2O5Adding the reaction raw material methyl levulinate and the reaction solvent in a mass ratio of 0.2:1:20 into a reactor, uniformly mixing, and introducing N before reaction2After air is removed, heating to 200 ℃ for reaction for 2h, after the reaction is finished, recovering a reaction solvent from a reaction system, centrifugally separating a lower-layer catalyst to obtain a product gamma-valerolactone, wherein the molar yield of the product gamma-valerolactone is 98.32% and the purity of the product gamma-valerolactone is 99.01%, precipitating and filtering the centrifugally separated lower-layer catalyst, washing the lower-layer catalyst by isopropanol, drying the lower-layer catalyst for 0.5h in vacuum at the temperature of 80 ℃, preserving the lower-layer catalyst in the atmosphere of N2, and using the lower-layer catalyst as the catalyst for next repeated use.
The reaction solvent is isopropanol and simultaneously serves as a reaction raw material hydrogen source, and is evaporated and recovered at the temperature of 80 ℃ under the condition of vacuum pumping of 0.084MPa after the reaction is finished, and then is circularly cooled by ice water to serve as the reaction solvent.
Example 2 the procedure of example 1 was followed, but the reaction temperature was 160 deg.C, and a molar yield of gamma-valerolactone of 13.17% and a product purity of 20.44% were obtained.
EXAMPLE 3 the procedure of example 1 was followed, but the reaction temperature was 180 ℃ and the gamma valerolactone molar yield was 86.49% with a product purity of 92.04%.
Example 4 the procedure of example 1 was followed, but the reaction temperature was 220 deg.C, the gamma valerolactone molar yield was 98.51%, and the product purity was 99.02%.
Example 5 the procedure of example 1 was followed, but the reaction temperature was 240 ℃ and a molar yield of gamma valerolactone of 98.84% and a product purity of 99.03% were obtained.
Example 6 the procedure of example 1 was followed, but the reaction time was 4 hours, and gamma-valerolactone was obtained in a molar yield of 97.92% and a product purity of 97.55%.
Example 7 the procedure of example 1 was followed, but the reaction time was 6 hours, resulting in a molar yield of gamma-valerolactone of 95.02% and a product purity of 96.57%.
EXAMPLE 8 the procedure of example 1 was followed, except that the reaction time was 8 hours, and gamma-valerolactone was obtained in a molar yield of 88.45% and a product purity of 92.25%.
EXAMPLE 9 the procedure of example 1 was followed, except that the reaction time was 10 hours, and thus, the molar yield of gamma-valerolactone was 88.44% and the product purity was 92.51%.
EXAMPLE 10 the procedure of example 1 was followed to prepare Nb (HC) as a catalyst raw material2O4)5And ZrOCl2·8H2The molar ratio of O is 0:1, the molar yield of the gamma-valerolactone is 62.02 percent, and the product purity is 65.16 percent.
EXAMPLE 11 the procedure of example 1 was followed, but Nb (HC) as a catalyst raw material was prepared2O4)5And ZrOCl2·8H2The molar ratio of O is 0.43:1, the molar yield of the gamma-valerolactone is 87.56%, and the product purity is 91.37%.
EXAMPLE 12 the procedure of example 1 was followed, but Nb (HC) as a catalyst raw material was prepared2O4)5And ZrOCl2·8H2The molar ratio of O is 1:1, the molar yield of the gamma-valerolactone is 82.92%, and the product purity is 89.45%.
EXAMPLE 13 procedure of example 1 was repeated to prepare Nb (HC) as a catalyst raw material2O4)5And ZrOCl2·8H2The molar ratio of O is 2.3:1,the mol yield of the gamma-valerolactone is 20.68 percent, and the product purity is 33.43 percent.
EXAMPLE 14 the procedure of example 1 was followed, but Nb (HC) as a catalyst raw material was prepared2O4)5And ZrOCl2·8H2The molar ratio of O is 4:1, the molar yield of the gamma-valerolactone is 20.00 percent, and the product purity is 31.26 percent.
EXAMPLE 15 the procedure of example 1 was followed, but Nb (HC) as a catalyst raw material was prepared2O4)5And ZrOCl2·8H2The molar ratio of O is 1:0, the molar yield of the gamma-valerolactone is 16.97%, and the product purity is 25.91%.
EXAMPLE 16 the procedure of example 1 was followed, but ZrO was used as it is2-Nb2O5The carrier is used as a catalyst (the mass percent of the active component Co in the catalyst is 0 percent), the molar yield of the gamma-valerolactone is 50.91 percent, and the product purity is 74.54 percent.
Example 17 the procedure is the same as example 1, but the mass percent of the active component Co in the catalyst is 5%, the molar yield of gamma-valerolactone is 77.33%, and the product purity is 87.19%.
Example 18 the procedure is the same as example 1, but the mass percent of the active component Co in the catalyst is 15%, the molar yield of gamma-valerolactone is 91.46%, and the product purity is 92.58%.
Example 19 the procedure was the same as in example 1, except that the catalyst contained 20% by weight of Co as the active component, and the molar yield of gamma-valerolactone was 90.76% and the product purity was 92.65%.
EXAMPLE 20 the procedure of example 1 was followed, except that the reaction solvent was absolute methanol, and gamma-valerolactone was obtained in a molar yield of 3.13% and a product purity of 6.15%.
EXAMPLE 21 the procedure of example 1 was followed, except that the reaction solvent was absolute ethanol, and gamma-valerolactone was obtained in a molar yield of 19.11% and a product purity of 25.76%.
EXAMPLE 22 the procedure of example 1 was followed, except that the reaction solvent was n-propanol, whereby gamma-valerolactone was obtained in a molar yield of 11.23% and a product purity of 27.23%.
EXAMPLE 23 the procedure of example 1 was followed, except that n-butanol was used as the reaction solvent, to give gamma-valerolactone in a molar yield of 32.79% and a product purity of 58.15%.
EXAMPLE 24 the procedure of example 1 was followed, except that the reaction solvent was isobutanol, to give gamma-valerolactone in a molar yield of 42.90% and a product purity of 61.29%.
EXAMPLE 25 the procedure of example 1 was followed, except that the catalyst was recycled for the 2 nd cycle, and gamma-valerolactone was obtained in a molar yield of 98.08% and a product purity of 98.81%.
EXAMPLE 26 the procedure of example 1 was followed, except that the catalyst was recycled for the 4 th time, and gamma-valerolactone was obtained in a molar yield of 97.92% and a product purity of 98.69%.
EXAMPLE 27 the procedure of example 1 was followed, except that the catalyst was recycled at 6 th time, and gamma-valerolactone was obtained in a molar yield of 97.87% and a product purity of 98.57%.
EXAMPLE 28 the procedure of example 1 was followed, except that the catalyst was recycled for the 8 th time, and gamma valerolactone was obtained in a molar yield of 97.55% and a product purity of 97.83%.
EXAMPLE 29 the procedure of example 1 was followed, except that the catalyst was recycled for the 10 th time, and gamma-valerolactone was obtained in a molar yield of 95.83% and a product purity of 96.59%.
TABLE 1 operating conditions and reaction results for examples 1-29
Note: in examples 25, 26, 27, 28 and 29, the recovered catalysts in the 2 nd, 4 th, 6 th, 8 th and 10 th times were dried under vacuum and recycled.
Claims (1)
1. A method for catalytically synthesizing gamma-valerolactone by using a cobalt-based hydrogenation catalyst is characterized by comprising the following steps of:
(1) the cobalt-based hydrogenation catalyst is Co/ZrO2-Nb2O5Wherein the mass percent of the active component Co is 10 percent, ZrO2-Nb2O5The molar ratio of Nb to Zr in the carrier is 0.2-0.25: 1;
the cobalt-based hydrogenation catalyst is of a spherical mesoporous structure, the aperture is 10-15 nm, and the pore volume is 0.16-0.24 cm3A specific surface area of 52 to 75 m/g2/g；
The cobalt-based hydrogenation catalyst Co/ZrO2-Nb2O5Medium, ZrO2Has rich oxygen vacancy and low-coordination oxygen ion, and passes through H before the catalyst is used2Reduced, reduced active component Co attracts ZrO2The oxygen atom on the ZrO undergoes a migration change to attract the ZrO2Oxygen on the catalyst activates Zr-O-Zr bonds to form-O-Zr vacancies, so that the surface of the catalyst is in a relative electron-deficient state, and the surface of the catalyst in the relative electron-deficient state can effectively activate the hydrogenation of C = O groups in methyl levulinate molecules in the process of catalyzing the hydrogenation of methyl levulinate to synthesize gamma-valerolactone;
the cobalt-based hydrogenation catalyst Co/ZrO2-Nb2O5Nb with large acid content and strong acidity2O5ZrO of metal oxide doped with acid-base amphiprotic2ZrO formed2-Nb2O5A carrier, which increases the acid sites and acid amount of the catalyst, and Nb-free Co/ZrO2Acid amount of 3.75mmol/g, Co/ZrO after Nb doping2-Nb2O5The acid amount of (a) is 4.95 mmol/g;
the cobalt-based hydrogenation catalyst Co/ZrO2-Nb2O5Nb species in the active components Co and ZrO2-Nb2O5The interaction between carriers inhibits the agglomeration of the active component Co and the carbon deposition sintering, and improves the dispersion degree of the active component Co, and the comparison of the attached drawings 2(a) and (b) in the specification shows that the active component Co is compared with Co/ZrO2Co/ZrO after Nb doping2-Nb2O5The active component Co is uniformly dispersed without obvious agglomerationLike;
the cobalt-based hydrogenation catalyst Co/ZrO2-Nb2O5In the medium, the doped Nb species makes ZrO2The crystal lattice is distorted to form ZrO2More oxygen vacancies are generated, the cationic oxophilic sites formed by the doped Nb species and the carbonyl oxygen in the methyl levulinate generate stronger interaction to weaken the C = O bond, reduce the energy required for breaking the C = O double bond in the methyl levulinate and enhance the catalytic hydrogenation performance: example 10 the results show Co/ZrO undoped with Nb2The mole yield of the catalytic methyl levulinate hydrogenation product gamma-valerolactone is 62.02%, and the result of example 1 shows that the Co/ZrO after doping Nb2-Nb2O5The molar yield of the catalytic methyl levulinate hydrogenation product gamma-valerolactone is 98.32%;
the cobalt-based hydrogenation catalyst Co/ZrO2-Nb2O5After the catalytic methyl levulinate hydrogenation reaction, recovering the catalytic methyl levulinate through simple centrifugal separation, and drying the catalytic methyl levulinate in a drying oven at the temperature of 60-80 ℃ and the vacuum degree of 100-133 Pa for 1-2 hours to obtain the catalytic methyl levulinate which can be used as a catalyst for the next repeated use without high-temperature calcination regeneration;
compared with the reported Ru/C, Cu/ZrO2、Ni/CeO2-ZrO2、Co/La2O3The catalyst activity is greatly reduced after the catalyst is repeatedly used for 3 times, and the results of example 29 show that the Co-based hydrogenation catalyst Co/ZrO2-Nb2O5The catalyst is repeatedly used for 10 times, still has better catalytic activity, and the mole yield of the gamma-valerolactone of the methyl levulinate hydrogenation product is still kept at 95.83%;
(2) the Co-based hydrogenation catalyst Co/ZrO as described in (1)2-Nb2O5Is prepared by the following method:
the first step is as follows: mixing Nb (HC)2O4)5And ZrOCl2·8H2Adding deionized water according to the molar ratio of 0.2-0.25: 1 into the O, stirring and dissolving to form a mixed solution with the total molar concentration of 0.10-0.15 mol/L, slowly adding ammonia water to control the pH value of the mixed solution to be within the range of 11-14, and stirring at room temperature for 30-40 min to obtain a mixed solution containing white precipitates;
the second step is that: transferring the mixed solution containing the white precipitate into a polytetrafluoroethylene lining, crystallizing at 170-180 ℃ for 6-8 h, cooling to room temperature, carrying out suction filtration and precipitation, washing a filter cake to be neutral by using deionized water, drying the obtained white powdery filter cake at 80-110 ℃ for 6-8 h, placing the white powdery filter cake in a box-type muffle furnace, raising the temperature to 450-500 ℃ at the rate of 2-3 ℃/min, roasting for 4-6 h, and cooling to obtain the ZrO2-Nb2O5A carrier;
the third step: mixing Co (NO)3)2·6H2O, ZrO prepared as described above2-Nb2O5Adding a carrier and an impregnant into a reactor according to a mass ratio of 0.1-0.2: 1: 15-20, soaking and stirring for 6-8 hours at 40-60 ℃, and evaporating and recovering the impregnant at 40-60 ℃ to obtain light purple powder, wherein the impregnant is absolute methanol or absolute ethanol;
the fourth step: drying the light purple powder at the constant temperature of 60-80 ℃ for 4-6 h, roasting the dried light purple powder in a box-type muffle furnace at the temperature rise rate of 2-3 ℃/min to 350-450 ℃ for 4-6 h, and cooling to obtain black powder, namely the cobalt-based hydrogenation catalyst Co/ZrO2-Nb2O5；
The prepared cobalt-based hydrogenation catalyst Co/ZrO2-Nb2O5Placing the mixture in a tubular furnace, raising the temperature to 450-500 ℃ at the heating rate of 3-5 ℃/min for 2 hours under the atmosphere of hydrogen flow rate of 45-55 mL/min, cooling, and placing the mixture in N2Passivating in an atmosphere for use in N2The catalytic activity of the catalyst can be effectively maintained for 45-60 days in the atmosphere;
(3) Co/ZrO from the cobalt-based hydrogenation catalyst described in (1)2-Nb2O5The method for synthesizing gamma-valerolactone by catalyzing methyl levulinate comprises the following steps:
Co/ZrO based hydrogenation catalyst2-Nb2O5Adding the reaction raw material methyl levulinate and the reaction solvent in a mass ratio of 0.1-0.2: 1:20 into a reactor, uniformly mixing, heating to 220-240 ℃ for reaction for 2 hours, recovering the reaction solvent from the reaction system after the reaction is finished, and centrifugally separating out the catalyst at the lower layer to obtain the product gamma-valerolactone, wherein the product gamma-valerolactone is gamma-valerolactoneThe molar yield is 95-98.8%, the purity is 96.5-99%, the centrifugally separated catalyst at the lower layer is precipitated and filtered, the precipitated and filtered catalyst is washed by isopropanol and then is dried in vacuum, and the catalyst can be used as a catalyst for the next time for reuse;
the reaction solvent is isopropanol and simultaneously serves as a reaction raw material hydrogen source, and after the reaction is finished, the isopropanol is evaporated and recovered at the temperature of 80-85 ℃ under the condition of vacuum pumping of 0.084-0.0848 MPa, and the cooled isopropanol serves as the reaction solvent for recycling.
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| CN115591541A (en) * | 2022-09-13 | 2023-01-13 | 吉林大学（Cn） | CeO doped with high-valence niobium metal ions 2 Preparation method and application thereof |
| CN115536495A (en) * | 2022-10-12 | 2022-12-30 | 河北工业大学 | Method for preparing 1, 4-pentanediol |
| CN115536495B (en) * | 2022-10-12 | 2023-12-15 | 河北工业大学 | Method for preparing 1, 4-pentanediol |
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Application publication date: 20201030 |